The Preparation and Reactions of the Isomeric Styrene Bromohydrins

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ff f i PE»ABAMON AHD SMGTXOHS OF THE ISOMERIC

tsrm m bbgmohydbxhs

lay John Edward Maurer

A t h e s i s subm itted i n p a r t i a l f u lf illm e n t o f th e re q u ire * manta f o r th e degree o f Doctor o f 'Philosophy i n th e Department of Chemistry i n th e Graduate College o f th e S ta te U n iv e rsity o f Iowa February* 1950

ProQuest Number: 10666180

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A0EHOTOSMEMENf

T his in v e s tig a tio n was c a r r ie d o u t under th e guidance o f Dr B obert K» Buckles*

The a u th o r w ishes to

e g r e s s h i s s in c e re a p p re c ia tio n to Dr Buckles f o r h i a many h e lp fu l suggestions* c o n sta n t I n t e r e s t , and encouragem ent,

TABLE OP OOOTBBttS Bag© SH&ODQWXOI , ...........

. . . ..............

HXST0R10AL

1 v

m s o u s a io i

....2

. ...................... —

P re p a ra tio n o f c^Ph©nyl~ t>-Broraoetbyl A lcohol and th e D eterm ination o f I t s S tru c tu re . .................. 7 P re p a ra tio n o f ^ P h e n y l* P-Bromoethyl A lcohol and th e D eterm ination o f i t s S tru c tu re • ................ 21 B rom inatlon o f E s te rs MPERXMEHTAL

................ ................. , ...........

P re p a ra tio n o f o£-ph©nyl~ P ~bromo e th y l a l c o h o l

29 54 54

A* S tyrene * aqueous bromine method . . . . . . . . . 34 B» S ty ren e * I^bromoacetsmid© method . . . . . . . . 5 5 0. R eduction w ith a l w l u m is o p r o p o x id e 36 D. Magnesium bromide * sty re n e oxide method .............. 37 E. Lithium bromide - sty re n e oxide method . . . 3 8 Attem pted p re p a ra tio n o f ^ p h e n y l- ^*brom oethyl a le o h o l ......................... A. B.

S ty ren e * M^bromoacetemide method . . . . . . . . 3 9 Fhenacyl bromide - aluminum is o propoxlde method .......... 39

P re p a ra tio n o f A* B. 0.

y?~ph©nyl~ £ ~bromo e th y l a l c o h o l

40

P re p a ra tio n o f ^ -p h e n y le th y l form ate . . . . 4 0 B rom ination o f -/?-p h e n y le th y l format© . . , . 4 2 R eactio n o f y?-p h en y l- /3 -brom oothyl format© w ith m ethyl a lc o h o l ........... 42

A ttem pted p re p a ra tio n o f # -p h en y l- i»ii*»innn.*

alco h o l

bromine method (1) * A two

A

l i t e r , th re e -n e c k e d f l a s k ©quipped with, a dropping funnel* a m echanical s t i r r e r , a r e f lu x condenser and a thermometer was h e a te d over a steam bath*

I n th e f la s k was p laced

500 m l. o f w ater and when th e tem perature had reached 90°, f iv e su cc essiv e p o rtio n s o f f iv e grams each o f sty re n e was added.

A fte r each su c c e ssiv e p o rtio n o f s ty re n e was added,

th e m ix tu re was thoroughly e m u lsifie d by vigorous s t i r r i n g and a 7 p e rc e n t s o lu tio n o f bromine In aqueous 10 p e rc e n t potassium bromide was added u n t i l th e attain m en t o f a yellow tin t* The p ro d u ct was e x tra c te d w ith e th e r and th e e th e r was removed by v&oum.

The r e s u lt in g amber co lo red

l i q u id was d i s t i l l e d a t 9 6 -9 7 °/! mm*, 109-110°/2 am ,, I1 7 -1 2 0 °/4 mm*, o r 129-130°/© mm.

d i s t i l l a t i o n o f th e com­

pound above 130° was im p ra c tic a l because o f ex cessiv e au to c a ta ly s e d decom position*

The compound was very la c h ry ­

m atory and th e t o t a l y ie ld was 46*1 g* (92$). The 3 ,5 -d in itro b e n so a t© o f t h i s compound m elts a t 92-95°,

35 B-«

S ta re m * H -brom oacetm lde m ethod,

T-o- a

o n e - l i t e r , th re e -n e c k f l a s k equipped w ith a m ercury-sealed s t i r r e r , a dropping fu n n el and a r e f lu x condenser was added 13*8 g* o f ff-b rw o a c o t amid© (1 2 ), 50 ml* o f w ate r, 50 m l. o f f r e s h ly p u r i f i e d dioxane, and a tr a c e o f p-toluen© su lfo n ic acid*

A fter s t i r r i n g f o r fir© m in u tes, th e s o lu tio n became

yellow i n color*

t h i s yellow c o lo r was presum ably due to

th e p re se n ce o f hypobromous a c id .

To t h i s yellow s o lu tio n

10,4 g. of sty re n e was added dropw ise.

I f th e a d d itio n i s

to o f a s t , a l l o f th e yellow c o lo r dlsm ppears* stan d in g th e c o lo r g ra d u a lly r e tu r n s .

However, on

I f th e sty ren e was

added slowly enough* th e s o lu tio n would r e t a i n th e yellow co lo r u n t i l th e r e a c tio n had gone to completion*

A fte r a l l

th e s ty re n e was added, th e s o lu tio n was s t i r r e d fo r f i f t e e n m inutes longer*

By this-, time th e s o lu tio n had become color**

l e s s and a heavy la y e r had se p a ra te d o u t,

T his two phase

m ixture was. e x tra c te d w ith e th e r and a f te r removal of th e ether-dioxan© s o lv e n t, th© compound was d i s t i l l e d a t reduced p re s s u r e , 110-11 4 °/4 “ ■

waa 16,6 g. (63$).

The 3 ,5 -d in ltro b e n s o a te o f t h i s ’m olts a t 90-91° and a m ix tu re w ith th e s mm e s t e r o f o(-phenyl--j?-brom oethyl a lco h o l a ls o m e lts a t 90- 91°.

m

Q* icd n o tlcm w ith

iao p ro p o x ld e* T h is

p ro ced u re i s a m o d ific a tio n o f th a t d e sc rib e d b j Lund ( 5 ,7 ) . To> a 500 ml# f la s k h o ld in g a r e f lu x condenser was added 15 g, o f aluminum* 0 .5 g# o f m ercu ric c h lo rid e and 300 m l, o f dry iao p ro p y l alcohol.-

The m ix tu re was h e a te d to b o ilin g and

0 ml#- 'o f carbon te t r a c h lo r id e added.

I t was th en re flu x e d

fo r f i v e h o u rs m& th e warm s o lu tio n was tr a n s f e r r e d to a 500 m l. c la ls e n f la s k f i t t e d w ith a p a r t i a l condenser f i l l e d w ith b o ilin g m ethyl a lc o h o l.

A fte r 20 g# o f phsnaeyl bromide

i n 100 ml# o f d ry iso p ro p y l a lc o h o l was added to t h i s flask * th e r e a c tio n m ix tu re was h e a te d to b o ilin g f o r 20 minuteg> During t h i s tim e no e f f o r t was made to d i s t i l l any o f th e acetone t h a t was formed.

At th e end o f t h i s tim e th e is o ­

p ro p y l a lc o h o l was r a p id ly removed a t reduced p re ssu re and th e rem aining a lc o h o la te was hydrolysed w ith 45 ml* o f hydro­ c h lo ric a c id in ' 20O m l. o f w ater,

The aqueous suspension

was e x tra c te d w ith e th e r and th e e th e r removed under reduced p re s s u re .

D i s t i l l a t i o n gave about one gram o f d i s t i l l a t e

b o ilin g a t 82°/3 mm, and 12 .6 g* {62*5$) a t lQ 6-108°/3 smu The 3* 5 -d in ltro b e n a o a te o f th e low b o ilin g f r a c tio n m elted a t 107-108°#

A m ix tu re o f t h i s e s t e r and th e same

e s t e r p re p a re d from